CN114716115B - Method for enhancing wetland denitrification based on anaerobic ammonia oxidation - Google Patents

Method for enhancing wetland denitrification based on anaerobic ammonia oxidation Download PDF

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CN114716115B
CN114716115B CN202210516520.2A CN202210516520A CN114716115B CN 114716115 B CN114716115 B CN 114716115B CN 202210516520 A CN202210516520 A CN 202210516520A CN 114716115 B CN114716115 B CN 114716115B
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wetland
filler
particle filler
water
concentration
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CN114716115A (en
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徐善文
赵立军
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Red Fungus Biology Guangdong Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/28—Anaerobic digestion processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/14—NH3-N
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/15—N03-N
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Abstract

The invention relates to the technical field of sewage treatment, in particular to a method for enhancing wetland denitrification based on anaerobic ammonia oxidation, which comprises the following steps of S1 filler preparation, S2 particle filler modification, S3 wetland bacterial biofilm formation and S4 natural wetland anaerobic ammonia oxidation bacteria enrichment. The invention provides a method for strengthening wetland denitrification based on anaerobic ammonia oxidation, which has low investment, high benefit and low energy consumption, wherein after being treated by anaerobic ammonia oxidizing bacteria enriched in a reactor, water eutrophic wetland has a nitrogen treatment rate as high as 90 percent, thereby strengthening the degradation capability of the wetland on pollutants, increasing denitrification functional microorganisms on the premise of not damaging and polluting the wetland and establishing a good wetland aquatic ecosystem.

Description

Method for enhancing wetland denitrification based on anaerobic ammonia oxidation
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a method for strengthening wetland denitrification based on anaerobic ammonia oxidation.
Background
In recent years, with the rapid development of China, the use of nitrogen is increased, and the eutrophication of water bodies is serious due to external pollution sources (artificial activities), internal sources (release of sediments) and hydrodynamic conditions (water body flow velocity and local circulation) of part of wetland ecosystems. The wetland ecosystem has certain self-cleaning capability due to abundant species, thereby ensuring the harmony of the system. However, in recent years, it is often necessary to intervene in the water body to improve the water body recovery ability.
For example, the intensified river purification equipment developed in japan mainly treats and purifies water in a river water purification facility by using gravity generated by the fall of a river channel, and then discharges the water out of the equipment, thereby achieving the dual purposes of purification and land saving. However, wetland ecosystem is different from river, most of wetland has not as good water flow rate as river, so some strengthening technology for river is not suitable for wetland system. The transfer, transformation and degradation of pollutants in water are carried out by utilizing cultured organisms or cultured and inoculated microorganisms, so that the water body is recovered. The biological-ecological restoration technology can strengthen the self-purification capacity and the material circulation rule of the water environment under the condition of not damaging and secondarily polluting the natural environment, and is a technology with low investment, high benefit, low energy consumption, low operation cost and great development potential.
For example, chinese patent CN2018100249671 discloses a method for constructing an enhanced denitrification artificial wetland, an artificial wetland and an enhanced denitrification method, wherein an underflow artificial wetland bed is excavated in a sewage area to be treated, and the enhanced denitrification treatment of sewage is performed by using the artificial wetland of the present invention, which comprises the steps of uniformly distributing water from a top plant planting area, and then performing heterotrophic denitrification treatment by using a corncob filler area; then carrying out autotrophic denitrification treatment in a sulfur filling area, and carrying out heterotrophic and autotrophic combined treatment to achieve deep denitrification and achieve sewage denitrification efficiency; although the technical method is simple to operate and easy to manage, and greatly improves the deep denitrification performance of the artificial wetland on the tail water of the sewage plant, the overall denitrification efficiency is poor due to the general performance of the used filler, and the requirement cannot be well met in practical use.
Disclosure of Invention
The invention aims to provide a method for enhancing wetland denitrification based on anaerobic ammonia oxidation, which improves the overall performance of a filler by carrying out a series of treatments on the filler so as to achieve the effect of improving the denitrification efficiency and solve the problems in the background art.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for enriching anaerobic ammonia oxidizing bacteria of a natural wetland comprises the following steps:
preparation of S1 Filler
Strip-shaped filler: mixing the wetland sediment, the pore-forming agent and the forming agent at 40-90 ℃, continuously stirring until the mixture is muddy, making strips of 10-50cm, drying the prepared strips at 80-110 ℃ for 10-15h, placing the strips in a muffle furnace, preheating to 50-500 ℃ in the air atmosphere, preheating and preserving heat for 20-60min, roasting to 1000-1200 ℃ at the speed of 1-5 ℃/min, preserving heat for 50-100min, cooling the strips to room temperature, and taking out the samples to obtain strip fillers;
particle filler: mixing the wetland sediment, the pore-forming agent and the forming agent at 40-90 ℃, continuously stirring to mud shape, preparing spherical particles of 5-15cm, drying the prepared particles at 80-110 ℃ for 10-15h, placing a sample in a muffle furnace, preheating to 50-500 ℃ in the air atmosphere, carrying out preheating and heat preservation for 20-60min, roasting to 1000-1200 ℃ at the speed of 1-5 ℃/min, carrying out heat preservation for 50-100min, cooling the ceramic particles to room temperature, taking out the sample, and obtaining the particle filler;
the particle filler is also pretreated before modification, and the specific operations are as follows:
1) Plasticating the solution-polymerized styrene-butadiene rubber for 3-7min by using a Haake internal mixer, then adding silicon dioxide particles into the internal mixer in two steps, mixing the silicon dioxide particles with the solution-polymerized styrene-butadiene rubber for 30-50min, controlling the temperature to be 80-90 ℃, the rotating speed of a rotor to be 70-100rpm, and the mold filling rate to be 75-80%, naturally cooling the mixed rubber to room temperature, calendering the cooled sample and dicumyl peroxide for 10-15 times by using a double-roll open mill, then calendering the mixed rubber for 10-15 times by using a double-roll open mill again for back mixing, finally vulcanizing and molding the mixed rubber by using a flat vulcanizing machine, wherein the temperature is 170-175 ℃, the pressure is 15-18MPa, and the vulcanizing time is 2-5min, crushing the vulcanized product, and sieving by using a 200-400-mesh sieve to obtain composite particles;
2) Adding the particle filler into an ethanol solution containing 1-10% of polyvinyl alcohol, reacting for 2-7h at 120-130 ℃ under the continuous stirring of 150-260r/min, drying in a drying oven, then adding into an ethanol solution containing a silane coupling agent with the volume concentration of 1-10%, reacting for 2-5h at 20-60 ℃ under the continuous stirring of 80-130r/min, taking out, drying, adding into an ethanol solution containing 1-10% of composite material particles, and reacting for 3-8h at 60-90 ℃ to obtain the composite particle filler;
3) Placing the composite particle filler into a plasma treatment device, placing the composite particle filler into a discharge area with dielectric barrier discharge, subjecting the composite particle filler to air low-temperature plasma treatment under atmospheric pressure for 180-540s, and taking out a product after the treatment is finished, thus finishing the pretreatment of the particle filler;
modification of S2 particulate fillers
Adding a high-valence metal soluble salt solution into a beaker, controlling the molar concentration of metal ions in the solution to be 0.1-2mol/L, adding a ceramic particle filler at 50-100 ℃ for reaction for 3-6h, taking out the modified particle filler after the reaction is finished, cleaning the modified particle filler until the solution is clear, and drying the solution at 80-110 ℃ for 6-20h. Putting the dried modified ceramic particle filler into a muffle furnace, heating to 350-800 ℃ at the speed of 1-5 ℃/min, preserving the heat for 1-5h, cooling to room temperature, and taking out to obtain a modified particle filler;
s3 wetland bacterial biofilm
Adding the modified particle filler prepared in the step S2 and sediments taken from the natural wetland according to the volume ratio of 1 (1-100), artificially simulating water distribution to prepare inlet water, and realizing biofilm formation of anaerobic ammonium oxidation bacteria by controlling the operation parameters of the reactor;
the modified particle filler is further treated, and the specific operations are as follows:
1) Mixing glycidyl trimethacrylate and sulfuric acid, placing the mixture in a water bath at 50-55 ℃ for heating for 3-7h, adding sodium periodate, placing the mixture in a dark place for 1-5h at room temperature, dropwise adding the treated glycidyl trimethacrylate into methanol in which sodium hydroxide and glucosamine hydrochloride are dissolved, simultaneously adding sodium cyanoborohydride, stirring until the solution becomes transparent liquid, evaporating the transparent liquid to a paste under reduced pressure, sealing and filling nitrogen, and placing the paste at 3-6 ℃ for storage to obtain glucosamine;
2) Adding a hydrochloric acid solution into the modified particle filler, carrying out 100-300W ultrasonic treatment for 20-40min, soaking for 10-15h, repeatedly washing with deionized water to neutrality, drying, mixing with dimethyl azodiisobutyrate overnight, repeatedly washing with methanol, adding a reaction solution consisting of cuprous chloride, N, N, N ', N', N '' -pentamethyldiethylenetriamine, copper chloride and glucosamine, reacting for 20-30h at room temperature, repeatedly washing with methanol after the reaction is finished, and drying;
s4 natural wetland anaerobic ammonium oxidation bacteria enrichment
The granular filler after bacteria biofilm formation of the S3 wetland and the long filler in the S1 are added, filling the mixed materials into a wire netting according to the proportion of a quantity ratio of 100;
the reactor device used for simulating the natural wetland ecosystem comprises a water inlet, an overflow weir, a riparian zone soil partition plate, a water outlet, a side water outlet hole and a bottom sewage discharge hole;
the wire netting is placed at the position of the soil partition plate on the river bank.
Furthermore, the long-strip filler comprises 50-90% of wetland sediment, 4-26% of pore-forming agent and 6-24% of forming agent in percentage.
Furthermore, in the particle filler, the components comprise, by percentage, 50-90% of wetland sediment, 4-26% of pore-forming agent and 6-24% of forming agent.
Furthermore, the pore-forming agent is composed of ammonium bicarbonate and wood chips according to a mass ratio of 1:1-5.
Furthermore, the forming agent consists of polyvinyl chloride and absolute ethyl alcohol according to the mass ratio of 1:5-10.
Furthermore, the mass ratio of the solution polymerized styrene-butadiene rubber, the nano silicon dioxide and the dicumyl peroxide is 100 (10-50) to 0.2-0.5.
Furthermore, the mass ratio of the particle filler to the ethanol solution is 1:2-3.
Further, the high valence metal soluble salt solution is at least one selected from aluminum chloride and ferric chloride.
Further, the operating parameters of the reactor are: the pH value is 7.5-8.0, the dissolved oxygen is 0.2-0.5mg/L, and the ratio of NH4+ -N and NO 2-N of the inlet water is controlled to be 0.8-1.1.
Furthermore, the artificial simulation water distribution is used as the water inlet of the inoculation device, the water is continuously fed through the pump, and when the filler of the inoculation module is red, the success of enrichment of the anaerobic ammonium oxidation bacteria is marked.
Further, the artificial simulation of the water distribution concentration sets NH 4 + N concentration of 0.30-1.00mg/L, NO 2 - N concentration of 0.01-0.10mg/L, NO 3 - The concentration of N is 0.20-1.50mg/L, the concentration of TN is 2.00-4.00mg/L, the concentration of TP is 0.05-0.15mg/L, and the concentration of COD is 5.00-10.00mg/L.
Furthermore, the proportion of the glycidyl trimethacrylate, the sulfuric acid, the sodium periodate, the methanol and the sodium cyanoborohydride is (1-10) mL, (0.1-1) mL, (0.3-0.8) mL, (20-50) mL, (10-30) mmol.
Furthermore, the concentration of the sulfuric acid is 0.2-0.5mol/L, and the concentration of the sodium periodate is 10-20mmol/L.
Furthermore, 0.4-1.0g of sodium hydroxide and 2-3g of glucosamine hydrochloride are dissolved in every 20-50mL of methanol.
Furthermore, the ratio of the modified particle filler to hydrochloric acid is 1 to 30g/mL, and the concentration of the hydrochloric acid is 1.0 to 1.5mol/L.
Further, the dimethyl azodiisobutyrate is used in an amount of 0.1 to 1.0% by mass of the modified particulate filler.
Furthermore, the reaction solution comprises 0.01-0.05mol/L cuprous chloride, 0.01-0.03mol/L LN, N, N ', N', N '' -pentamethyldiethylenetriamine, 0.001-0.003mol/L cupric chloride and 2-3mol/L glucosamine.
Furthermore, the ratio of the modified particle filler to the reaction solution is 1.
Furthermore, the feeding liquid at the water inlet is artificially simulated for water distribution, and the region between the overflow weirs at the two sides of the water inlet and the water outlet is a main reaction region.
Furthermore, the riparian zone soil partition plate is used for isolating riparian zone soil and wetland water and simulating an ecosystem of a riparian zone water-soil interface.
Furthermore, the side water outlet holes and the bottom sewage discharge holes reasonably simulate the influence of natural wetland flooding river water and tidal change (coastal wetland) on nitrogen migration and conversion.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, nano-scale silica particles are added into a solution polymerized styrene-butadiene rubber matrix, nano-scale nanoparticles are aggregated to form submicron aggregates, adjacent aggregates are connected with each other to form a micron-scale filler network, and the nano-silica has good dispersibility, so that the compactness of the aggregates is reduced, the branching degree is improved, the adjacent aggregates are easy to be mutually overlapped to form large-size high-branching-degree aggregates, and a high-connectivity network structure is formed in the formed composite material; in addition, the silane coupling agent is adopted to carry out surface treatment on the particle filler, the particle filler is grafted with amino and oxygen-containing groups, the bonding between the particle filler and the composite material is enhanced, and the interface strength is improved, so that the porous structure of the particle filler is further enhanced, the particle filler has a more stable high-porosity structure, and the high-activity surface of the particle filler is more beneficial to the enrichment of anaerobic ammonium oxidation bacteria; meanwhile, the formed composite particle filler is treated by adopting a low-temperature plasma technology, a high-strength external electric field accelerates free electrons in the composite particle filler and endows the energy to the free electrons to be high-energy electrons, the high-energy electrons transmit the energy to other ion groups, atoms or molecules through an inelastic collision process, the obtained energy ion groups, atoms or molecules are excited to form free radicals or active groups with strong oxidizability, active ions with strong oxidizability are contacted with organic matters to react, the organic matters are oxidized and decomposed into small molecular compounds, the high-energy electrons can also directly act on the organic matters, the high-energy electrons break chemical bonds of the organic matters after inelastic collision, and the broken chains or open rings of the organic matters are finally degraded, so that the efficient denitrification capability of the sewage is realized.
According to the invention, a surface initiation-atom transfer radical polymerization method is utilized, glucosamine with double bonds is taken as a monomer, a high-density polymer is grafted on the surface of modified particles in situ to form a compact hydrophilic polymer layer, and the glycan structure contains a large amount of hydroxyl groups, so that the hydrophilicity of the modified particle filler is obviously improved while the better mechanical strength of the modified particle filler is maintained, the enrichment of anammox bacteria in the later period is facilitated, and the polymer layer also provides a carbon source for the growth and the propagation of the anammox bacteria, so that the propagation of the anammox bacteria is facilitated, and the rapid enrichment of the anammox bacteria on the surface of the modified filler particles is realized.
The invention provides a method for strengthening wetland denitrification based on anaerobic ammonia oxidation, which has low investment, high benefit and low energy consumption, wherein after being treated by anaerobic ammonia oxidizing bacteria enriched in a reactor, water eutrophic wetland has a nitrogen treatment rate as high as 90 percent, thereby strengthening the degradation capability of the wetland on pollutants, increasing denitrification functional microorganisms on the premise of not damaging and polluting the wetland and establishing a good wetland aquatic ecosystem.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the description below are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic view of the apparatus of the present invention;
FIG. 2 shows the diversity of anammox bacteria in the packing, wherein (a) is the surface of the packing and (b) is the interior of the packing;
FIG. 3 shows the change of the average nitrogen removal rate before and after the anaerobic ammonia oxidation biofilm culturing filler is added;
in figure 1, 1 is a water inlet; 2. an overflow weir; 3. a riparian zone soil barrier; 4. a water outlet; 5. a lateral water outlet hole; 6. bottom part and a sewage draining hole.
Detailed Description
The following description of the embodiments of the present invention is provided by way of specific examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein. The invention is capable of other and different embodiments and its several details are capable of modifications and/or changes in various obvious respects, all without departing from the spirit of the present invention.
It should be understood that the process equipment or apparatus not specifically mentioned in the following examples and experimental examples are conventional in the art.
Example 1
A method for enriching anaerobic ammonia oxidizing bacteria of a natural wetland comprises the following steps:
preparation of S1 Filler
Strip-shaped filler: mixing 50% of wetland sediment, 26% of pore-forming agent and 24% of forming agent at 40 ℃, continuously stirring until the mixture is muddy, preparing 10cm long strips, drying the prepared long strips at 80 ℃ for 10 hours, placing the dried long strips in a muffle furnace to preheat to 150 ℃ in the air atmosphere, preheating and preserving heat for 20min, roasting to 1000 ℃ at the speed of 1 ℃/min, preserving heat for 50min, and taking out a sample when the long strips are cooled to room temperature to obtain long strip filler;
particle filler: mixing 50% of wetland sediment, 26% of pore-forming agent and 24% of forming agent at 40 ℃, continuously stirring until the mixture is muddy, preparing 5cm spherical particles, drying the prepared particles at 80 ℃ for 10h, placing a sample in a muffle furnace, preheating to 150 ℃ in the air atmosphere, carrying out preheating and heat preservation for 20min, roasting to 1000 ℃ at the speed of 1 ℃/min, carrying out heat preservation for 50min, cooling ceramic particles to room temperature, and taking out the sample to obtain a particle filler;
the particle filler is also pretreated before modification, and the specific operations are as follows:
1) Respectively weighing solution-polymerized styrene-butadiene rubber, nano-silica and dicumyl peroxide according to a mass ratio of 100:10, plasticating the solution-polymerized styrene-butadiene rubber for 3min by using a Haake internal mixer, adding silica particles into the internal mixer in two steps, mixing the silica particles with the solution-polymerized styrene-butadiene rubber for 30min, controlling the temperature to be 80 ℃, the rotating speed of a rotor to be 70rpm and the mold filling rate to be 75%, naturally cooling the mixed rubber to room temperature, calendering the cooled sample and the dicumyl peroxide for 10 times by using a double-roll open mill, calendering the mixed rubber for 10 times to carry out back mixing, vulcanizing and molding the mixed rubber by using a flat vulcanizing machine, wherein the temperature is 170 ℃, the pressure is 15MPa and the vulcanizing time is 2min, crushing the vulcanized product, and sieving the crushed product by using a 200-mesh sieve to obtain composite particles;
2) Controlling the mass ratio of the particle filler to the ethanol solution to be 1:2, adding the particle filler into the ethanol solution containing 1% of polyvinyl alcohol, reacting for 2 hours at 120 ℃ under the continuous stirring of 150r/min, drying in a drying oven, then adding the particle filler into the ethanol solution containing 1% of silane coupling agent by volume concentration, reacting for 2 hours at 20 ℃ under the continuous stirring of 80r/min, taking out and drying, adding the particle filler into the ethanol solution containing 1% of composite material particles, and reacting for 3 hours at 60 ℃ to obtain the composite particle filler;
3) Placing the composite particle filler into a plasma treatment device, placing the composite particle filler into a discharge area with dielectric barrier discharge, subjecting the composite particle filler to air low-temperature plasma treatment under atmospheric pressure for 180s, and taking out a product after the treatment is finished, thus finishing the pretreatment of the particle filler;
modification of S2 particulate fillers
Adding a high-valence metal soluble salt solution into a beaker, controlling the molar concentration of metal ions in the solution to be 0.1mol/L, adding a particle filler at 50 ℃ for reaction for 3 hours, taking out the modified particle filler after the reaction is finished, cleaning until the solution is clear, drying at 80 ℃ for 6 hours, putting the dried modified particle filler into a muffle furnace, heating to 350 ℃ at the speed of 1 ℃/min, preserving heat for 1 hour, cooling to room temperature, and taking out to obtain the modified particle filler;
s3 wetland bacterial biofilm
Adding the modified particle filler prepared in the step S2 and sediments taken from the natural wetland according to the mass ratio of 1;
the modified particle filler is further treated, and the specific operations are as follows:
1) Mixing 1mL of glycidyl trimethacrylate and 0.1mL of sulfuric acid with the concentration of 0.2mol/L, placing the mixture in a water bath at 50 ℃ for heating for 3h, adding 0.3mL of sodium periodate with the concentration of 10mmol/L, placing the mixture at room temperature in a dark place for 1h, dropwise adding the treated glycidyl trimethacrylate into 20mL of methanol in which 0.4g of sodium hydroxide and 2g of glucosamine hydrochloride are dissolved, simultaneously adding 10mmol of sodium cyanoborohydride, stirring until the solution becomes transparent liquid, evaporating the solution under reduced pressure to form a paste, sealing, filling nitrogen, and placing the paste at 3 ℃ for storage to obtain glucosamine;
2) Adding 1.0mol/L hydrochloric acid solution into a modified particle filler according to the proportion of 1.
S4 natural wetland anaerobic ammonium oxidation bacteria enrichment
Filling the granular filler subjected to bacterial biofilm formation in the S3 wetland and the long filler in the S1 into a wire netting according to the proportion of a quantity ratio of 100;
the reactor device used for simulating the natural wetland ecosystem comprises a water inlet, an overflow weir, a riparian zone soil partition plate, a water outlet, a side water outlet hole and a bottom sewage discharge hole;
the wire netting is placed at the position of the soil partition plate on the river bank.
Furthermore, the pore-forming agent is composed of ammonium bicarbonate and wood chips according to a mass ratio of 1:1.
Furthermore, the forming agent is composed of polyvinyl chloride and absolute ethyl alcohol according to a mass ratio of 1:5.
Still further, the high valence soluble salt solution of a metal is selected from aluminum chloride.
Further, the operating parameters of the reactor are: pH of 7.5, dissolved oxygen of 0.2mg/L, control of feed water NH 4 + -N and NO 2 - The ratio of-N is 0.8.
Furthermore, the feeding liquid at the water inlet is artificially simulated for water distribution, and the area between the water inlet and the overflow weirs at the two sides of the water outlet is a main reaction area.
Furthermore, the riparian zone soil partition plate is used for isolating riparian zone soil and wetland water and simulating an ecosystem of a riparian zone water-soil interface.
Furthermore, the side water outlet holes and the bottom sewage discharge holes reasonably simulate the influence of natural wetland flooding river water and tidal change (coastal wetland) on nitrogen migration and conversion.
Furthermore, the artificial simulation water distribution is used as the water inlet of the inoculation device, the water is continuously fed through the pump, and when the filler of the inoculation module is red, the success of enrichment of the anaerobic ammonium oxidation bacteria is marked.
Further, the artificial simulation of the water distribution concentration sets NH 4 + N concentration of 0.30mg/L, NO 2 - N concentration of 0.01mg/L, NO 3 - The concentration of N is 0.20mg/L, the concentration of TN is 2.00mg/L, the concentration of TP is 0.05mg/L, and the concentration of COD is 5.00mg/L.
Example 2
A method for enriching anaerobic ammonia oxidizing bacteria of a natural wetland comprises the following steps:
preparation of S1 Filler
Strip-shaped filler: mixing 80% of wetland sediment, 10% of pore-forming agent and 10% of forming agent at 60 ℃, continuously stirring until the mixture is muddy, then preparing a strip of 20cm, drying the prepared strip at 100 ℃ for 12h, placing the dried strip in a muffle furnace to preheat to 300 ℃ in the air atmosphere, preheating and preserving heat for 30min, roasting to 1100 ℃ at the speed of 2 ℃/min, preserving heat for 70min, and taking out a sample after the strip is cooled to room temperature, thus obtaining a strip filler;
particle filler: mixing 80% of wetland sediment, 10% of pore-forming agent and 10% of forming agent at 60 ℃, continuously stirring until the mixture is mud-shaped, preparing 10cm spherical particles, drying the prepared particles at 100 ℃ for 12h, placing a sample in a muffle furnace, preheating to 300 ℃ in the air atmosphere, carrying out preheating and heat preservation for 30min, roasting to 1100 ℃ at the speed of 2 ℃/min, carrying out heat preservation for 70min, cooling ceramic particles to room temperature, taking out the sample, and obtaining the particle filler;
the particle filler is also pretreated before modification, and the specific operations are as follows:
1) Respectively weighing solution-polymerized styrene-butadiene rubber, nano-silica and dicumyl peroxide according to a mass ratio of 100;
2) Controlling the mass ratio of the particle filler to the ethanol solution to be 1.5, adding the particle filler into the ethanol solution containing 5% of polyvinyl alcohol, reacting for 5 hours at 125 ℃ under the continuous stirring of 200r/min, drying in an oven, then adding into the ethanol solution containing a silane coupling agent with the volume concentration of 5%, continuously stirring for 3 hours at 40 ℃ under 100r/min, taking out and drying, adding into the ethanol solution containing 5% of composite material particles, and reacting for 5 hours at 70 ℃ to obtain the composite particle filler;
3) Placing the composite particle filler into a plasma treatment device, placing the composite particle filler into a discharge area with dielectric barrier discharge, subjecting the composite particle filler to air low-temperature plasma treatment under atmospheric pressure for 360s, and taking out a product after the treatment is finished, thus finishing the pretreatment of the particle filler;
modification of S2 particulate fillers
Adding a high-valence metal soluble salt solution into a beaker, controlling the molar concentration of metal ions in the solution to be 1mol/L, adding a particle filler to react for 5 hours at 75 ℃, taking out the modified particle filler after the reaction is finished, cleaning until the solution is clear, drying for 15 hours at 100 ℃, putting the dried modified particle filler into a muffle furnace, heating to 600 ℃ at the speed of 3 ℃/min, preserving heat for 3 hours, cooling to room temperature, and taking out to obtain the modified particle filler;
s3 wetland bacterial biofilm
Adding the modified particle filler prepared in the step S2 and sediments taken from the natural wetland according to the mass ratio of 1;
the modified particle filler is further treated, and the specific operations are as follows:
1) Mixing 5mL of glycidyl trimethacrylate and 0.5mL of sulfuric acid with the concentration of 0.3mol/L, placing the mixture in a water bath with the temperature of 52 ℃ for heating for 5 hours, adding 0.5mL of sodium periodate with the concentration of 15mmol/L, placing the mixture at room temperature in a dark place for 3 hours, dropwise adding the treated glycidyl trimethacrylate into 40mL of methanol in which 0.8g of sodium hydroxide and 2.5g of glucosamine hydrochloride are dissolved, simultaneously adding 20mmol of sodium cyanoborohydride, stirring until the solution becomes transparent liquid, carrying out reduced pressure evaporation to dryness to obtain paste, sealing and filling nitrogen, and placing the paste at the temperature of 5 ℃ for storage to obtain glucosamine;
2) Adding 1.3mol/L hydrochloric acid solution into a modified particle filler according to the proportion of 1.
S4 natural wetland anaerobic ammonium oxidation bacteria enrichment
The granular filler after the bacteria of the wetland S3 are coated and the strip filler in S1, filling the wire netting according to the proportion of 50;
the reactor device used for simulating the natural wetland ecosystem comprises a water inlet, an overflow weir, a riparian zone soil partition plate, a water outlet, a side water outlet hole and a bottom sewage discharge hole;
the wire netting is placed at the position of the soil partition plate on the river bank.
Furthermore, the pore-forming agent is composed of ammonium bicarbonate and wood chips according to a mass ratio of 1:2.
Furthermore, the forming agent is composed of polyvinyl chloride and absolute ethyl alcohol according to a mass ratio of 1:8.
Still further, the high valence soluble metal salt solution is selected from ferric chloride.
Further, the operating parameters of the reactor are: pH of 8.0, dissolved oxygen of 0.3mg/L, and NH of inlet water 4 + -N and NO 2 - The ratio of-N is 1.0.
Furthermore, the feeding liquid at the water inlet is artificially simulated for water distribution, and the region between the overflow weirs at the two sides of the water inlet and the water outlet is a main reaction region.
Furthermore, the riparian zone soil partition plate is used for isolating riparian zone soil and wetland water and simulating an ecosystem of a riparian zone water-soil interface.
Furthermore, the side water outlet holes and the bottom sewage discharge holes reasonably simulate the influence of natural wetland flooding river water and tidal change (coastal wetland) on nitrogen migration and conversion.
Furthermore, the artificial simulation water distribution is used as the water inlet of the inoculation device, the water is continuously fed through the pump, and when the filler of the inoculation module is red, the success of enrichment of the anaerobic ammonium oxidation bacteria is marked.
Further, the artificial simulation of the water distribution concentration sets NH 4 + N concentration of 0.7mg/L, NO 2 - N concentration of 0.08mg/L, NO 3 - The concentration of N is 1.2mg/L, the concentration of TN is 3mg/L, the concentration of TP is 0.1mg/L, and the concentration of COD is 7mg/L.
Example 3
A method for enriching anaerobic ammonia oxidizing bacteria of a natural wetland comprises the following steps:
preparation of S1 Filler
Strip-shaped filler: mixing 90% of wetland sediment, 4% of pore-forming agent and 6% of forming agent at 90 ℃, continuously stirring until the mixture is muddy, making a strip of 50cm, drying the prepared strip at 110 ℃ for 15h, placing the dried strip in a muffle furnace, preheating to 500 ℃ in the air atmosphere, preheating and preserving heat for 60min, roasting to 1200 ℃ at the speed of 5 ℃/min, preserving heat for 100min, and taking out a sample after the strip is cooled to room temperature to obtain a strip filler;
particle filler: mixing 90% of wetland sediment, 4% of pore-forming agent and 6% of forming agent at 90 ℃, continuously stirring until the mixture is muddy, preparing 15cm spherical particles, drying the prepared particles at 110 ℃ for 15h, placing a sample in a muffle furnace, preheating to 500 ℃ in the air atmosphere, carrying out preheating and heat preservation for 60min, roasting to 1200 ℃ at the speed of 5 ℃/min, carrying out heat preservation for 100min, cooling ceramic particles to room temperature, taking out the sample, and obtaining the particle filler;
the particle filler is also pretreated before modification, and the specific operations are as follows:
1) Respectively weighing solution-polymerized styrene-butadiene rubber, nano-silica and dicumyl peroxide according to a mass ratio of 100:50, plasticating the solution-polymerized styrene-butadiene rubber for 7min by using a Haake internal mixer, adding silica particles into the internal mixer in two steps, mixing the silica particles with the solution-polymerized styrene-butadiene rubber for 50min, controlling the temperature to be 90 ℃, the rotation speed of a rotor to be 100rpm, the mold filling rate to be 80%, naturally cooling the mixed rubber to room temperature, calendering the cooled sample and the dicumyl peroxide for 15 times by using a double-roll open mill, calendering the mixed rubber for 15 times to perform back mixing, vulcanizing and molding the mixed rubber by using a flat vulcanizing machine at the temperature of 175 ℃, the pressure of 18MPa and the vulcanization time of 5min, crushing the vulcanized product, and sieving the crushed product with a 400-mesh sieve to obtain composite particles;
2) Controlling the mass ratio of the particle filler to the ethanol solution to be 1:3, adding the particle filler into the ethanol solution containing 10% of polyvinyl alcohol, reacting for 7 hours at 130 ℃ under the continuous stirring of 260r/min, drying in a drying oven, then adding the particle filler into the ethanol solution containing 10% of silane coupling agent by volume concentration, reacting for 5 hours at 60 ℃ under the continuous stirring of 130r/min, taking out and drying, adding the particle filler into the ethanol solution containing 10% of composite material particles, and reacting for 8 hours at 90 ℃ to obtain the composite particle filler;
3) Placing the composite particle filler into a plasma treatment device, placing the composite particle filler into a discharge area with dielectric barrier discharge, subjecting the composite particle filler to air low-temperature plasma treatment under atmospheric pressure for 540s, and taking out a product after the treatment is finished, thus finishing the pretreatment of the particle filler;
modification of S2 particulate fillers
Adding a high-valence metal soluble salt solution into a beaker, controlling the molar concentration of metal ions in the solution to be 2mol/L, adding a particle filler at 100 ℃ for reaction for 6 hours, taking out the modified particle filler after the reaction is finished, cleaning until the solution is clear, drying at 110 ℃ for 20 hours, putting the dried modified particle filler into a muffle furnace, heating to 800 ℃ at the speed of 5 ℃/min, preserving heat for 5 hours, cooling to room temperature, and taking out to obtain the modified particle filler;
s3 wetland bacterial biofilm
Adding the modified particle filler prepared in the step S2 and sediments taken from the natural wetland according to the mass ratio of 1;
the modified particle filler is further treated, and the specific operations are as follows:
1) Mixing 10mL of glycidyl trimethacrylate and 1.0mL of sulfuric acid with the concentration of 0.5mol/L, placing the mixture in a water bath with the temperature of 55 ℃ for heating for 7 hours, adding 0.8mL of sodium periodate with the concentration of 20mmol/L, placing the mixture at room temperature in a dark place for 5 hours, dropwise adding the treated glycidyl trimethacrylate into 50mL of methanol in which 1.0g of sodium hydroxide and 3g of glucosamine hydrochloride are dissolved, simultaneously adding 30mmol of sodium cyanoborohydride, stirring until the solution becomes a transparent liquid, carrying out reduced pressure evaporation to dryness to obtain a paste, sealing and filling nitrogen, and placing the paste at the temperature of 6 ℃ for storage to obtain glucosamine;
2) Adding 1.5mol/L hydrochloric acid solution into a modified particle filler according to the proportion of 1.
S4 natural wetland anaerobic ammonium oxidation bacteria enrichment
Filling the granular filler subjected to bacterial biofilm formation in the S3 wetland and the long filler in the S1 into a wire netting according to the quantity ratio of 10;
the reactor device used for simulating the natural wetland ecosystem comprises a water inlet, an overflow weir, a riparian zone soil partition plate, a water outlet, a side water outlet hole and a bottom sewage discharge hole;
the wire netting is placed at the position of the soil partition plate on the river bank.
Furthermore, the pore-forming agent is composed of ammonium bicarbonate and wood chips according to a mass ratio of 1:5.
Furthermore, the forming agent is composed of polyvinyl chloride and absolute ethyl alcohol according to a mass ratio of 1.
Still further, the higher valent metal soluble salt solution is selected from aluminum chloride.
Further, the operating parameters of the reactor are: pH was 8.0, dissolved oxygen was 0.5mg/L, feed water NH was controlled 4 + -N and NO 2 - The ratio of-N is 1.1.
Furthermore, the feeding liquid at the water inlet is artificially simulated for water distribution, and the region between the overflow weirs at the two sides of the water inlet and the water outlet is a main reaction region.
Furthermore, the riparian zone soil partition plate is used for isolating riparian zone soil and wetland water and simulating an ecosystem of a riparian zone water-soil interface.
Furthermore, the side water outlet holes and the bottom sewage discharge holes reasonably simulate the influence of natural wetland flooding river water and tidal change (coastal wetland) on nitrogen migration and conversion.
Furthermore, the artificial simulation water distribution is used as the water inflow of the inoculation device, the water is continuously fed through the pump, and when the filler of the inoculation module is red, the successful enrichment of the anammox bacteria is marked.
Further, the artificial simulation of the water distribution concentration sets NH 4 + N concentration 1.00mg/L, NO 2 - N concentration of 0.10mg/L, NO 3 - The concentration of N is 1.50mg/L, the concentration of TN is 4.00mg/L, the concentration of TP is 0.15mg/L, and the concentration of COD is 10.00mg/L.
Comparative example 1: this comparative example is essentially the same technical solution as in example 1, except that the particulate filler is not pretreated prior to modification.
Comparative example 2: this comparative example is essentially the same technical solution as in example 1, except that the particulate filler is not treated after modification.
Comparative example 3: this comparative example is essentially the same technical solution as in example 1, except that the particulate filler is not pretreated before modification and treated after modification.
Test experiment 1:
the method in the embodiment 1 is adopted to respectively prepare the filler and modify the filler, and the particle filler is treated before modification and after modification, the reactor device used for simulating the wetland ecosystem is a stainless steel water tank with the length multiplied by the width multiplied by the height multiplied by 2m multiplied by 1m multiplied by 0.8m, and the whole device comprises a water inlet 1, an overflow weir 2, a riparian zone soil baffle plate 3, a water outlet 4, a side water outlet 5 and a bottom sewage discharge hole 6; the water inlet substrate is used for artificially simulating water distribution and is provided with NH 4 + N concentration of 0.50 mg. L-1,NO 2 - N concentration of 0.04 mg. L-1,NO 3 - A wetland aquatic ecosystem is to be constructed, wherein the N concentration is 0.70 mg.L-1, the TN concentration is 3.00 mg.L-1, the TP concentration is 0.09 mg.L-1, and the COD concentration is 8.00 mg.L-1; inoculating river sediment with MLSS of 2.5g/L, wherein the natural substrate comprises river sediment, riparian zone soil, aquatic plants, detritus, other particulate matters (such as weathered shellfish) and a small amount of fish and the like, and the plant species comprise emergent aquatic plants (Hua Kela Sa with the average plant height of 0.8m, reed and the like), floating plants (Eichhornia crassipes, pistia stratiotes and the like), submerged plants (bitter herbs, curly pondweed, watermifusleaf foxtail and the like) and the like; adding a small amount of the particle filler and the strip filler after bacteria biofilm formation of the laboratory wetland during the stable operation period of the reaction, wherein the fillers are filled according to the proportion of 100; controlling the reactor operating parameters, pH 7.5, dissolved oxygen at0.1mg/L, without an external temperature controller.
(1) Filler biofilm culturing flora
As shown in fig. 1, there are 4 known anammox species, ca. Brocadia, ca. Kuenenia, ca. Jettenia, and ca. Scalindua.
(2) Enhanced denitrification performance of anaerobic ammonia oxidation
The average nitrogen removal rate data before and after the anaerobic ammonia oxidation biofilm culturing filler is shown in the following figure 3.
The filler is added into the simulation reactor, so that the removal efficiency of nitrogen in the wetland can be improved, the TN average removal rate of the wetland can reach 98%, and compared with the removal rate of TN of a wetland simulation system without the anaerobic ammonium oxidation bacteria filler, the removal rate of TN is improved by more than 4 times.
Test experiment 2:
the method in the example 1 is adopted, the modified particle fillers in the example 1 and the comparative examples 1-2 are respectively selected for testing, and the tail water (the C/N ratio is less than or equal to 2, NO is less than or equal to 2) of the municipal sewage treatment plant is treated 3 -the mass concentration of N is 19-22 mg/L) is introduced into the reaction device through the water inlet, the reaction device is operated at the temperature of 25-28 ℃ until the effluent quality is stable by adjusting the water inflow and controlling the hydraulic retention time to be 10h, the effluent quality of the reaction device is monitored every day, the average values of the concentrations of COD, total nitrogen, ammonia nitrogen, total phosphorus, nitrate nitrogen, ammonium nitrogen and nitrite nitrogen of the effluent are detected, the corresponding removal rate is calculated, and the measurement results are shown in table 1.
Wherein, the Chemical Oxygen Demand (COD) in the water is detected according to HJ/T399-2007 fast digestion spectrophotometry for measuring the chemical oxygen demand of water quality; detecting Total Nitrogen (TN) in water according to GB11894-89 alkaline potassium persulfate digestion ultraviolet spectrophotometry for measuring total nitrogen in water; detecting ammonia Nitrogen (NH) in water according to HJ 535-2009 'measuring Nashin' reagent spectrophotometry for water ammonia nitrogen 4 + -N); nitrate Nitrogen (NO) in water is detected according to HJ/T346-2007 ultraviolet spectrophotometry for nitrate determination of water quality 3 - -N); detecting nitrite Nitrogen (NO) in water according to GB 7493-87 spectrophotometry for measuring nitrite in water 2 - -N) (ii) a Measurement of dissolved oxygen in water Dissolved Oxygen (DO) in water was detected by the hash membrane electrode method.
TABLE 1 measurement of the amount of wastewater and the quality of water before and after the wastewater treatment
Figure BDA0003638147270000141
Figure BDA0003638147270000151
As can be seen from Table 1, the conventional granular filler is subjected to a series of treatments, so that the anaerobic ammonium oxidation bacteria can be propagated and rapidly enriched, and the high-efficiency denitrification capability on sewage can be realized, wherein NO is 3 - The removal rate of-N can reach 94.16%, NH 4 + The removal rate of-N can reach 29.31 percent, and the total nitrogen removal rate can reach 93.35 percent.
The above description is only an example and an experimental example of the present invention, and is not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (7)

1. A method for strengthening wetland denitrification based on anaerobic ammonia oxidation is characterized by comprising the following steps:
preparation of S1 Filler
Strip-shaped filler: mixing the wetland sediment, the pore-forming agent and the forming agent at 40-90 ℃, continuously stirring until the mixture is muddy, making the mixture into a strip of 10-50cm, drying the prepared strip, placing the dried strip in a muffle furnace, preheating to 50-500 ℃ in the air atmosphere, carrying out preheating and heat preservation for 20-60min, roasting to 1000-1200 ℃ at the speed of 1-5 ℃/min, carrying out heat preservation for 50-100min, cooling the strip to room temperature, and taking out the sample to obtain a strip filler;
particle filler: mixing the wetland sediment, the pore-forming agent and the forming agent at 40-90 ℃, continuously stirring until the mixture is muddy, preparing spherical particles of 5-15cm, drying the prepared particles, placing the dried particles in a muffle furnace, preheating to 50-500 ℃ in the air atmosphere, carrying out preheating and heat preservation for 20-60min, roasting to 1000-1200 ℃ at the speed of 1-5 ℃/min, carrying out heat preservation for 50-100min, cooling the ceramic particles to room temperature, and taking out a sample to obtain a particle filler;
the particle filler is also pretreated before modification, and the specific operations are as follows:
1) Plasticating the solution-polymerized styrene-butadiene rubber for 3-7min by using a Haake internal mixer, then adding silicon dioxide particles into the internal mixer in two steps, mixing the silicon dioxide particles with the solution-polymerized styrene-butadiene rubber for 30-50min, controlling the temperature to be 80-90 ℃, the rotating speed of a rotor to be 70-100rpm, and the mold filling rate to be 75-80%, naturally cooling the mixed rubber to room temperature, calendering the cooled sample and dicumyl peroxide for 10-15 times by using a double-roll open mill, then calendering the mixed rubber for 10-15 times by using a double-roll open mill again for back mixing, finally vulcanizing and molding the mixed rubber by using a flat vulcanizing machine, wherein the temperature is 170-175 ℃, the pressure is 15-18MPa, and the vulcanizing time is 2-5min, crushing the vulcanized product, and sieving by using a 200-400-mesh sieve to obtain composite particles;
2) Adding the particle filler into an ethanol solution containing 1-10% of polyvinyl alcohol, reacting for 2-7h at 120-130 ℃ under the continuous stirring of 150-260r/min, placing the mixture in a drying oven for drying, then adding the mixture into an ethanol solution containing a silane coupling agent with the volume concentration of 1-10%, reacting for 2-5h at 20-60 ℃ under the continuous stirring of 80-130r/min, taking out the mixture and drying the mixture, then adding the mixture into an ethanol solution containing 1-10% of composite material particles, and reacting for 3-8h at 60-90 ℃ to obtain the composite particle filler;
3) Putting the composite particle filler into a plasma treatment device, placing the composite particle filler in a discharge area of dielectric barrier discharge, subjecting the composite particle filler to low-temperature plasma treatment of air under atmospheric pressure for 180-540s, and taking out a product after the treatment is finished, thus finishing the pretreatment of the particle filler;
wherein in the step 1), the mass ratio of the solution polymerized styrene-butadiene rubber, the nano silicon dioxide and the dicumyl peroxide is 100 (10-50) to 0.2-0.5;
in the step 2), the mass ratio of the particle filler to the ethanol solution is 1:2-3;
modification of S2 particulate fillers
Adding a high-valence metal soluble salt solution into a beaker, controlling the molar concentration of metal ions in the solution to be 0.1-2mol/L, adding a ceramic particle filler at 50-100 ℃ to react for 3-6h, taking out the modified particle filler after the reaction is finished, cleaning until the solution is clear, drying at 80-110 ℃ for 6-20h, putting the dried modified ceramic particle filler into a muffle furnace, heating to 350-800 ℃ at the speed of 1-5 ℃/min, preserving heat for 1-5h, cooling to room temperature, and taking out to obtain the modified particle filler;
the high valence metal soluble salt solution is at least one selected from aluminum chloride and ferric chloride;
s3 wetland bacterial biofilm
Adding the modified particle filler prepared in the step S2 and sediments taken from the natural wetland according to the volume ratio of 1 (1-100), artificially simulating water distribution to prepare inlet water, and realizing the biofilm formation of the anaerobic ammonium oxidation bacteria by controlling the operation parameters of the reactor;
s4 natural wetland anaerobic ammonium oxidation bacteria enrichment
The granular filler after bacteria biofilm formation of the S3 wetland and the long filler in the S1 are added, filling the wire netting according to the proportion of 100;
the reactor device used for simulating the natural wetland ecosystem comprises a water inlet, an overflow weir, a riparian zone soil partition plate, a water outlet, a side water outlet hole and a bottom sewage discharge hole;
the wire netting is placed at the position of the soil partition plate on the river bank.
2. The method for enhancing wetland denitrification based on anaerobic ammonia oxidation according to claim 1, characterized by comprising the following steps: in the step S1, the long-strip filler comprises 50-90% of wetland sediment, 4-26% of pore-forming agent and 6-24% of forming agent in percentage;
in the particle filler, the components comprise 50-90% of wetland sediment, 4-26% of pore-forming agent and 6-24% of forming agent in percentage;
the pore-forming agent consists of ammonium bicarbonate and wood chips according to a mass ratio of 1:1-5;
the forming agent consists of polyvinyl chloride and absolute ethyl alcohol according to a mass ratio of 1:5-10.
3. The method for enhancing wetland denitrification based on anaerobic ammonia oxidation according to claim 1, characterized by comprising the following steps: in step S3, the operating parameters of the reactor are: pH of 7.5-8.0, dissolved oxygen of 0.2-0.5mg/L, and NH of inlet water 4 + -N and NO 2 - -N is in the range of 0.8 to 1.1;
the artificial simulation water distribution is used as water inlet of the inoculation device, water is continuously fed through the pump, and when the filler of the inoculation module is red, the success of enrichment of anaerobic ammonium oxidation bacteria is marked;
the artificial simulation of the water distribution concentration is provided with NH 4 + N concentration of 0.30-1.00mg/L, NO 2 - N concentration of 0.01-0.10mg/L, NO 3 - The concentration of N is 0.20-1.50mg/L, the concentration of TN is 2.00-4.00mg/L, the concentration of TP is 0.05-0.15mg/L, and the concentration of COD is 5.00-10.00mg/L.
4. The method for enhancing wetland denitrification based on anaerobic ammonia oxidation according to claim 1, characterized by comprising the following steps: in step S3, the modified particulate filler is further treated, specifically, the following operations are performed:
1) Mixing glycidyl trimethacrylate and sulfuric acid, placing the mixture in a water bath at 50-55 ℃ for heating for 3-7h, adding sodium periodate, placing the mixture in a dark place for 1-5h at room temperature, dropwise adding the treated glycidyl trimethacrylate into methanol in which sodium hydroxide and glucosamine hydrochloride are dissolved, simultaneously adding sodium cyanoborohydride, stirring until the solution becomes transparent liquid, evaporating the transparent liquid to a paste under reduced pressure, sealing and filling nitrogen, and placing the paste at 3-6 ℃ for storage to obtain glucosamine;
2) Adding a hydrochloric acid solution into the modified particle filler, carrying out ultrasonic treatment for 20-40min at 100-300W, soaking for 10-15h, repeatedly washing with deionized water to neutrality, drying, mixing with dimethyl azodiisobutyrate overnight, repeatedly washing with methanol, adding a reaction solution consisting of cuprous chloride, N, N, N ', N ', N ' -pentamethyldiethylenetriamine, copper chloride and glucosamine, reacting for 20-30h at room temperature, repeatedly washing with methanol after the reaction is finished, and drying.
5. The method for enhancing wetland denitrification based on anaerobic ammonia oxidation according to claim 4, characterized by comprising the following steps: in the step 1), the proportion of the glycidyl trimethacrylate, the sulfuric acid, the sodium periodate, the methanol and the sodium cyanoborohydride is (1-10) mL (0.1-1) mL (0.3-0.8) mL (20-50) mL (10-30) mmol;
the concentration of the sulfuric acid is 0.2-0.5mol/L, and the concentration of the sodium periodate is 10-20mmol/L;
0.4-1.0g of sodium hydroxide and 2-3g of glucosamine hydrochloride are dissolved in each 20-50mL of methanol.
6. The method for enhancing wetland denitrification based on anaerobic ammonia oxidation according to claim 4, characterized by comprising the following steps: in the step 2), the ratio of the modified particle filler to hydrochloric acid is 1-30 g/mL, and the concentration of the hydrochloric acid is 1.0-1.5mol/L;
the dosage of the dimethyl azodiisobutyrate accounts for 0.1 to 1.0 percent of the mass of the modified particle filler;
the reaction solution consists of 0.01-0.05mol/L cuprous chloride, 0.01-0.03mol/L LN, N, N ', N ', N ' -pentamethyldiethylenetriamine, 0.001-0.003mol/L cupric chloride and 2-3mol/L glucosamine;
the ratio of the modified particle filler to the reaction liquid is 1-40 g/mL.
7. The method for enhancing wetland denitrification based on anaerobic ammonia oxidation according to claim 1, characterized by comprising the following steps: the feeding liquid at the water inlet is artificially simulated for water distribution, and the area between the water inlet and the overflow weirs at the two sides of the water outlet is a main reaction area;
the riparian zone soil partition plate is used for isolating riparian zone soil and wetland water and simulating an ecosystem of a riparian zone water-soil interface;
the side water outlet holes and the bottom sewage discharge holes reasonably simulate the influence of natural wetland flooding river water and tidal change on nitrogen migration and conversion.
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